Steven D. R. Christie

Preparation of highly substituted tetrahydropyrans via a metal assisted dipolar cycloaddition reaction

A range of highly substituted tetrahydropyrans have been prepared by reaction of a donor-acceptor cyclobutane, where the donor is a metal-alkyne complex, with an aldehyde under Lewis acid conditions.

Homologation of allylic alcohols. An approach to cyclic and acyclic polyoxygenated compounds

Abstract The combination of the Sharpless asymmetric epoxidation reaction with a sulfur ylide mediated synthesis of allylic alcohols from epoxides provides a powerful iterative process for the production of polyoxygenated compounds. The alkene installed in the sulfur ylide reaction has also been used in a number of ring closing metathesis reactions to produce highly oxygenated cyclic compounds.

Heterobimetallic alkyne complexes in organic synthesis: An asymmetric variant of the Pauson-Khand reaction

Abstract The use of heterobimetallic alkyne complexes for the synthesis of cyclopentenones is described. The inherent chirality of the complexes has been used to effect high levels of stereocontrol in transformations giving optically enriched organic end products.

Functionalisation of Ti6Al4V components fabricated using selective laser melting with a bioactive compound.

Surface modification of an implant with a biomolecule is used to improve its biocompatibility and to reduce post-implant complications. In this study, a novel approach has been used to functionalise phosphonic acid monolayers with a drug. Ti6Al4V components fabricated using selective laser melting (SLM) were functionalised with Paracetamol (a pharmaceutically relevant biomolecule) using phosphonic acid based self-assembled monolayers (SAMs). The attachment, stability of the monolayers on the SLM fabricated surface and functionalisation of SAMs with Paracetamol were studied using X-ray photoelectron spectroscopy (XPS) and surface wettability measurements. The obtained results confirmed that SAMs were stable on the Ti6Al4V surface for over four weeks and then began to desorb from the surface. The reaction used to functionalise the phosphonic acid monolayers with Paracetamol was noted to be successful. Thus, the proposed method has the potential to immobilise drugs/proteins to SAM coated surfaces and improve their biocompatibility and reduce post-implant complications.

Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications

Selective laser melting (SLM) has previously been shown to be a viable method for fabricating biomedical implants; however, the surface chemistry of SLM fabricated parts is poorly understood. In this study, X-ray photoelectron spectroscopy (XPS) was used to determine the surface chemistries of (a) SLM as-fabricated (SLM-AF) Ti6Al4V and (b) SLM fabricated and mechanically polished (SLM-MP) Ti6Al4V samples and compared with (c) traditionally manufactured (forged) and mechanically polished Ti6Al4V samples. The SLM-AF surface was observed to be porous with an average surface roughness (Ra) of 17.6±3.7μm. The surface chemistry of the SLM-AF was significantly different to the FGD-MP surface with respect to elemental distribution and their existence on the outermost surface. Sintered particles on the SLM-AF surface were observed to affect depth profiling of the sample due to a shadowing effect during argon ion sputtering. Surface heterogeneity was observed for all three surfaces; however, vanadium was witnessed only on the mechanically polished (SLM-MP and FGD-MP) surfaces. The direct and indirect 3T3 cell cytotoxicity studies revealed that the cells were viable on the SLM fabricated Ti6Al4V parts. The varied surface chemistry of the SLM-AF and SLM-MP did not influence the cell behaviour.

3D printed fluidics with embedded analytic functionality for automated reaction optimisation

Additive manufacturing or ‘3D printing’ is being developed as a novel manufacturing process for the production of bespoke micro- and milliscale fluidic devices. When coupled with online monitoring and optimisation software, this offers an advanced, customised method for performing automated chemical synthesis. This paper reports the use of two additive manufacturing processes, stereolithography and selective laser melting, to create multifunctional fluidic devices with embedded reaction monitoring capability. The selectively laser melted parts are the first published examples of multifunctional 3D printed metal fluidic devices. These devices allow high temperature and pressure chemistry to be performed in solvent systems destructive to the majority of devices manufactured via stereolithography, polymer jetting and fused deposition modelling processes previously utilised for this application. These devices were integrated with commercially available flow chemistry, chromatographic and spectroscopic analysis equipment, allowing automated online and inline optimisation of the reaction medium. This set-up allowed the optimisation of two reactions, a ketone functional group interconversion and a fused polycyclic heterocycle formation, via spectroscopic and chromatographic analysis.

An Investigation of the Behavior of Solvent based Polycaprolactone ink for Material Jetting

An initial study of processing bioresorbable polycaprolactone (PCL) through material jetting was conducted using a Fujifilm Dimatix DMP-2830 material printer. The aim of this work was to investigate a potential solvent based method of jetting polycaprolactone. Several solvents were used to prepare a PCL solvent based ink and 1, 4-dioxane was chosen with the consideration of both solubility and safety. The morphology of PCL formed under different substrate temperatures, droplet spacings were investigated. Multi-layer PCL structures were printed and characterized. This work shows that biodegradable polycaprolactone can be processed through material jetting.

A new photocrosslinkable polycaprolactone-based ink for three-dimensional inkjet printing.

A new type of photocrosslinkable polycaprolactone (PCL) based ink that is suitable for three-dimensional (3D) inkjet printing has been developed. Photocrosslinkable Polycaprolactone dimethylacrylate (PCLDMA) was synthesized and mixed with poly(ethylene glycol) diacrylate (PEGDA) to prepare an ink with a suitable viscosity for inkjet printing. The ink performance under different printing environments, initiator concentrations, and post processes was studied. This showed that a nitrogen atmosphere during printing was beneficial for curing and material property optimization, as well as improving the quality of structures produced. A simple structure, built in the z-direction, demonstrated the potential for this material for the production of 3D printed objects. Cell tests were carried out to investigate the biocompatibility of the developed ink.

A tunable nanopore sensor for the detection of metal ions using translocation velocity and biphasic pulses

A tunable resistive pulse sensor, utilising a polyurethane nanopore, has been used to characterise nanoparticles as they traverse the pore opening. Herein we demonstrate that the translocation speed, conductive and resistive pulse magnitude, can be used to infer the surface charge of a nanoparticle, and act as a specific transduction signal for the binding of metal ions to ligands on the particle surface. Surfaces of silica nanoparticles were modified with a ligand to demonstrate the concept, and used to extract copper(ii) ions (Cu2+) from solution. By tuning the pH and ionic strength of the solution, a biphasic pulse, a conductive followed by a resistive pulse is recorded. Biphasic pulses are becoming a powerful means to characterise materials, and provide insight into the translocation mechanism, and herein we present their first use to detect the presence of metal ions in solution. We demonstrate how combinations of translocation speed and/or biphasic pulse behaviour are used to detect Cu2+ with quantitative responses across a range of pH and ionic strengths. Using a generic ligand this assay allows a clear signal for Cu2+ as low as 1 ppm with a short 5-minute incubation time, and is capable of measuring 10 ppm Cu2+ in the presence of 5 other ions. The method has potential for monitoring heavy metals in biological and environmental samples.

A New Photocrosslinkable Polycaprolactone based ink for 3D Inkjet Printing

A new type of photocrosslinkable polycaprolactone (PCL) based ink that is suitable for three-dimensional (3D) inkjet printing has been developed. Photocrosslinkable Polycaprolactone dimethylacrylate (PCLDMA) was synthesized and mixed with poly(ethylene glycol) diacrylate (PEGDA) to prepare an ink with a suitable viscosity for inkjet printing. The ink performance under different printing environments, initiator concentrations, and post processes was studied. This showed that a nitrogen atmosphere during printing was beneficial for curing and material property optimization, as well as improving the quality of structures produced. A simple structure, built in the z-direction, demonstrated the potential for this material for the production of 3D printed objects. Cell tests were carried out to investigate the biocompatibility of the developed ink.